CN103781546B - For the preparation of the method for the V-Ti-P catalyst of synthesis 2,3-unsaturated carboxylic acid - Google Patents

For the preparation of the method for the V-Ti-P catalyst of synthesis 2,3-unsaturated carboxylic acid Download PDF

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CN103781546B
CN103781546B CN201280044845.XA CN201280044845A CN103781546B CN 103781546 B CN103781546 B CN 103781546B CN 201280044845 A CN201280044845 A CN 201280044845A CN 103781546 B CN103781546 B CN 103781546B
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catalyst
titanium
acid
carbon monoxide
water
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CN103781546A (en
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D.W.诺尔曼
G.C.塔斯丁
M.J.S.纳什
邓榴
T.S.史密斯
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Eastman Chemical Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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Abstract

The present invention relates to the carbon monoxide-olefin polymeric of the mixed oxide comprising vanadium, titanium and phosphorus.Described titanium component derived from water soluble, the organic titanic compound of redox active.It is highly effective that described carbon monoxide-olefin polymeric is prepared on acrylic acid (particularly using industrial relevant waterborne liquid charging) at promotion formaldehyde to the vapour phase condensation of acetic acid.

Description

For the preparation of the method for the V-Ti-P catalyst of synthesis 2,3-unsaturated carboxylic acid
Invention field
The present invention relates generally to catalytic field, and be specifically related to the mixed oxide catalyst for the preparation of 2,3-unsaturated carboxylic acid.
Background technology
2,3-unsaturated carboxylic acid and ester can by formaldehyde (H 2cO) originate and comprise the saturated carboxylic acid of a few carbon atom or the reaction preparation of ester.Therefore, acrylic acid and methacrylic acid derivative can be prepared by the condensation of formaldehyde source and acetic acid or propanoic derivatives respectively.Described reaction is for the water of the carboxylic acid derivates generation monovalent of every monovalent of reaction.
Although propose multiple catalysts for this reaction, the catalyst comprising acid vanadium and phosphorous oxides is the most effective, especially when there is the third component such as titanium or silicon in the catalyst.But water trends towards the condensation reaction suppressing to use these catalyst.Therefore, formalin (it comprises the formaldehyde of about 37wt% usually in water) is used to be inefficient as parent material.Methyl alcohol also can be the inhibitor of condensation reaction, and also can comprise methyl alcohol due to formalin, and efficiency can be lowered further.When carboxylic acid is reactant, in formalin, the existence of methyl alcohol can produce the mixture of acid and methyl ester.And when ester is reactant, the water in formalin can produce the mixture of acid and ester.
The formalin of technical grade comprises the formaldehyde of about 55wt%.It is relatively cheap, and is therefore the source of finance of this reactant.Therefore, exist in this area in the gas phase formaldehyde and alkanoic acid or ester condensation being tolerated the demand of the catalyst of the water in feed.Ideally, this catalyst also will provide high formaldehyde conversion and the high selectivity for acrylic acid product.
Vanadium-titanium-phosphorus (V-Ti-P) mixed oxide generates acrylic acid catalyst known most by the condensation of formaldehyde and acetic acid.But the preparation of these catalyst may be dangerous and be unsuitable for scale.Usually by first hydrolyzed liquid titanium chloride, titanium component is incorporated in these catalyst.Unfortunately, this step can produce a large amount of salt acid mists.Therefore, also exist in this area for safer and be more suitable for the industrial demand preparing the method for V-Ti-P mixed oxide catalyst.
The present invention solves these and other demand, and it will be apparent by following description and claim.
summary of the invention
In first aspect, the invention provides the carbon monoxide-olefin polymeric of the mixed oxide comprising vanadium (V), titanium (Ti) and phosphorus (P).The titanium component of this carbon monoxide-olefin polymeric derived from water soluble, the organic titanic compound of redox active.
In second aspect, the invention provides the method that preparation comprises the carbon monoxide-olefin polymeric of the mixed oxide of vanadium (V), titanium (Ti) and phosphorus (P).The method comprises the following steps:
(a) providing package containing water soluble, the aqueous solution of the organic titanic compound of redox active;
B vfanadium compound and phosphorus compound join in the aqueous solution of this titanium to form the mixture of catalytic component by ();
C () heats this mixture;
D () removes water to obtain the solid residue comprising described catalytic component from heat-treated mixture; With
E () calcines this solid residue in the presence of air at elevated temperatures to obtain carbon monoxide-olefin polymeric.
In the third aspect, the invention provides the method for preparation 2,3-unsaturated carboxylic acid.The method makes formaldehyde source contact to obtain the step of 2,3-unsaturated carboxylic acid with carboxylic acid under the existence of condensation catalyst under being included in vapour phase condensation condition.Described condensation catalyst comprises the mixed oxide of vanadium (V), titanium (Ti) and phosphorus (P).The titanium component of described condensation catalyst derived from water soluble, the organic titanic compound of redox active.
brief Description Of Drawings
Fig. 1 is the figure of the X-ray diffraction pattern showing the amorphous catalyst prepared by method A in embodiment 1.
Fig. 2 is the figure of the X-ray diffraction pattern being presented at the amorphous catalyst prepared by method B in comparative example 1.
Fig. 3 be presented at the mixing prepared by method C in comparative example 2 amorphous-crystallization (TiO 2) figure of X-ray diffraction pattern of catalyst.
Fig. 4 is presented in comparative example 3 by crystallization [VO (HPO prepared by method D 4) (H 2o) 0.5] figure of X-ray diffraction pattern of catalyst.
Fig. 5 is presented in comparative example 4 by crystalline catalysts [(VO) prepared by method E 2(P 2o 7)] the figure of X-ray diffraction pattern.
Fig. 6 is presented in comparative example 5 by crystalline catalysts (TiO prepared by method F 2) the figure of X-ray diffraction pattern.
Fig. 7 is the figure of the X-ray diffraction pattern showing the amorphous catalyst prepared by method G in example 2.
Fig. 8 is presented in comparative example 6 by crystalline catalysts [V (PO prepared by method H 3) 3with Ti (P 2o 7)] the figure of X-ray diffraction pattern.
Fig. 9 is the figure of the X-ray diffraction pattern being presented at the amorphous catalyst prepared by method I in embodiment 5.
Figure 10 is the figure of the X-ray diffraction pattern being presented at the amorphous catalyst prepared by method J in embodiment 6.
detailed Description Of The Invention
Be surprised to find that V-Ti-P mixed oxide catalyst can by water soluble, the organic titanium of redox active originates preparation.Adopt this titanium source can provide safer inherently and more practical and route faster for V-Ti-P material.In addition, be surprised to find that the catalyst obtained can have higher surface area and acidity, and when use aqueous formaldehyde source and acetic acid are as can be higher for acrylic acid formation activity during charging.
Therefore, in first aspect, the invention provides the carbon monoxide-olefin polymeric of the mixed oxide comprising vanadium (V), titanium (Ti) and phosphorus (P).The titanium component of described carbon monoxide-olefin polymeric derived from water soluble, the organic titanic compound (being sometimes called " titanium compound of water soluble ", " organic titanic compound " or " titanium compound " in this article simply) of redox active.
As used herein, when for two or more article a series of, term "and/or" refer in the article listed any one can be used alone, maybe can adopt two or more any combination in the article listed.Such as, if composition is described to comprise component A, B and/or C, so composition can comprise independent A; Independent B; Independent C; The combination of A and B; The combination of A and C; The combination of B and C, or the combination of A, B and C.
Should be appreciated that mention that one or more method step is not precluded within merging described step before or after there is other method step or there is buffering technique step between those step explicitly pointed out especially.In addition, except as otherwise noted, the alpha code of method step or composition be a kind of identify discontinuous behavior or composition facilitate means, and described alpha code can arrange with any order.
Water soluble, refer to that organic titanic compound can be dissolved in the water the homogeneous solution of the organic titanic compound forming at least 1wt% under 20 DEG C and 1atm absolute pressure (101.325kPa).Preferably, described compound can dissolve the homogeneous solution forming at least 25wt% in water.More preferably, this compound can dissolve the homogeneous solution forming at least 40wt% in water.
Redox active refers to that the oxidation state of vanadium can be reverted to+4 by+5 by the organic ligand of organic titanic compound, reverts to+3, or revert to+3 by+4 by+5.If or for the preparation of in the aqueous mixture of catalyst, the oxidation state of vanadium can be reverted to+4 by+5 by the derivative of organic titanic compound, reverts to+4, or revert to+3 by+4 by+5, and so this organic titanic compound is " redox active ".
Water soluble, the example of the organic titanic compound of redox active comprises lactic acid titanium, alkanolamine titanium and titanium acetylacetone.These compounds are commercially available, such as, be purchased with trade name TYZOR by DorfKetal.The example of the practicality of these compounds comprise two (2 hydroxy propanoic acid) two hydroxide two ammonium close titanium (IV) (titanium(IV) bis (ammoniumlactate) dihydroxide) (TBALDH), diethanol amine titanium, triethanolamine titanium and titanium acetylacetone.In one aspect, organic titanic compound comprise two (2 hydroxy propanoic acid) two hydroxide two ammonium close titanium (IV).
Catalyst according to the invention composition can have general formula VTi ap bo c, wherein a=0.3-6.0, preferred 1.0-4.0; B=2.0-13.0, preferred 4.0-10.0; With c be the component met outside oxygen chemical valence needed for atomicity.
Carbon monoxide-olefin polymeric of the present invention can load on oxide carrier.Suitable oxide carrier comprises silica, aluminium oxide, titanium oxide, zirconia and Titanium pyrophosphate or zirconium.Also can use other oxide, condition is them is inertia for the catalytic reaction expected.Carrier should be physics durable with preformed.Term " preform " is used to refer to that the shape of final catalyst and raw material carrier are substantially identical in this context.Preformed oxide can have the average grain diameter of diameter about 0.1 millimeter (mm) to about 20mm usually.They can with any common form, such as extrudate, compression pellet or ground to form the loose material of required mesh size.They also can be various shape, such as bar-shaped, star, cylindrical, spherical or fault block.
Catalyst according to the invention composition structurally can be mainly unbodied.Those skilled in the art will know that amorphous catalyst composition can have a small amount of crystal structure such as caused by impurity." unbodied " or " mainly unbodied " refers to that carbon monoxide-olefin polymeric comprises the crystalline material being less than 10wt%.Crystallinity percentage calculates based on the integrated intensity of the X-ray diffraction from independent diffraction pattern, and the peak being greater than the crystallite dimension of 30 is defined as crystal, and the peak being less than or equal to the crystallite dimension of 30 is defined as amorphous.
According to a second aspect of the invention, catalyst according to the invention composition can use following general step to prepare:
(a) providing package containing water soluble, the aqueous solution of the organic titanic compound of redox active;
B vfanadium compound and phosphorus compound join in the aqueous solution of this titanium to form the mixture of catalytic component by ();
C () heats this mixture;
D () removes water to obtain the solid residue comprising described catalytic component from heat-treated mixture; With
E () calcines this solid residue in the presence of air at elevated temperatures to obtain carbon monoxide-olefin polymeric.
The aqueous solution comprising the titanium compound of water soluble can directly be obtained by industrial source maybe can by the preparation that is dissolved in the water by titanium compound.The concentration of the titanium aqueous solution can change in wide region.Such as, this solution can have 25-75wt%, or the titanium compound concentration of 30-70wt% or 50-60wt%.
Mode vfanadium compound and phosphorus compound being joined the titanium aqueous solution is not particularly limited.Such as, vfanadium compound and phosphorus compound can be blended together and form physical mixture or product, join afterwards in the aqueous solution of titanium.Or V and P-compound can add successively with any order or join in the aqueous solution of titanium simultaneously.Therefore, vfanadium compound and phosphide " add " to refer to and add vfanadium compound and phosphorus compound respectively by as used herein statement, or jointly add as the physical mixture of the two or the product as the two.
Similarly, heat treatment step and water remove step and can carry out successively or simultaneously.Such as, when by distill or evaporate remove water, heat treatment step can distillation or evaporation during occur.
Described heat treatment step can be carried out in wide temperature range, such as, from being greater than environment temperature to being up to 200 DEG C or higher.The object of heat treatment step promotes mixing in catalyst precarsor and/or reaction.Depend on adopted catalyst precarsor and temperature, described heat treatment step can carry out a few minutes to a few hours or a couple of days.
Water removes step and can complete in many ways.Such as, as the above mentioned, water can remove by distilling or evaporating.Or as discussed in greater detail below, catalytic component can by adding to anti-solvent in mixture to be settled out catalytic component and described precipitation to be separated to obtain solid residue from liquid and to be precipitated out from solution.Then by decant or filtration, water can be removed.
After water removes step (it can comprise follow-up drying steps), can pulverize obtaining solid residue and sieve to obtain required particle diameter.Before use the catalyst granules be sieving through can be calcined in atmosphere in one or more stage subsequently.Calcining heat is usually the scope of 200-800 DEG C.Preferably, calcining heat is 300-500 DEG C.Calcining step carries out 1 to 10 hour usually, and preferred 2-8 hour.After calcining, define according to mixed oxide catalyst of the present invention.
Except the titanium compound of above-mentioned water soluble, catalyst precarsor can be the ammonium salt of vanadium, titanium and phosphorus, halide, oxyacid, oxysalt, hydroxide or oxide.In one aspect of the invention, carbon monoxide-olefin polymeric with comprise two (2 hydroxy propanoic acid) two hydroxide two ammonium close titanium (IV) organic titanic compound preparation.
Described vfanadium compound is preferably water soluble.The example of these compounds comprises vanadium trichloride, vanadic sulfate (IV) hydrate and optionally with the ammonium vanadate of oxalic acid aqueous solution and/or lactic acid aqueous solution process.Also the vanadium of other water soluble can be used to originate.
Described phosphorus compound is also preferably water soluble.Upon calcination, this compound should be converted into phosphorous oxides.These phosphorus compounds comprise the ammonium salt of phosphoric acid, phosphorous acid and these acid.
Reproducibility compound can be joined in reactant mixture to give the carbon monoxide-olefin polymeric that obtains extra surface area.For preferred lactic acid this object, but also can use other compound with difunctional (that is, difunctional compound), such as citric acid, glycolic, oxalic acid, ethylene glycol, butanediol, hexylene glycol or pentanediol.The use of these surface area reagent is optional, but normally preferred.In one aspect of the invention, difunctional compound can add in the mixture of catalytic component before heat treatment step (c).In one aspect of the invention, difunctional compound comprises lactic acid.
Prepare the actual example of of the method for catalyst according to the invention composition to comprise the aqueous solution of the TBALDH of 50wt% and ammonium metavanadate and phosphorus aqueous acid, and optionally lactic acid, mixing; Under agitation add hot mixt at 130 DEG C; By distillation, water is removed from heat-treated mixture; And in atmosphere at 300 DEG C then at the residue that 450 DEG C of calcinings obtain.
Or, according to another embodiment of the invention, carbon monoxide-olefin polymeric can be prepared as mentioned above, is by non-increasing soluble solvent miscible for water after heat treatment step, or " anti-solvent ", join in reaction/heating container to be settled out most of catalytic component.Like this, the water by distilling the energy-intensive of carrying out can be avoided to remove, and carbon monoxide-olefin polymeric can calcine collection subsequently instead by filtration.Described anti-solvent can be polar compound, such as alcohol, ketone, aldehyde, ether or ester.Preferred alcohols (as ethanol) is as anti-solvent.
Carbon monoxide-olefin polymeric can have general formula VTi ap bo c, wherein a=0.3-6.0, preferred 1.0-4.0; B=2.0-13.0, preferred 4.0-10.0; With c be the component met outside oxygen chemical valence needed for atomicity.
Carbon monoxide-olefin polymeric of the present invention can load on oxide carrier.Suitable oxide carrier comprises silica, aluminium oxide, titanium oxide, zirconia and Titanium pyrophosphate or zirconium.Also can use other oxide, condition is them for the catalytic reaction of hope is inertia.Carrier should be that physics is durable and preformed.Term " preform " is used to refer to that the shape of final catalyst and raw material carrier are substantially identical within a context.Preformed oxide can have the average grain diameter of diameter about 0.1 millimeter (mm) to about 20mm usually.They can with any common form, such as extrudate, compression pellet or ground to form the prose style free from parallelism of required mesh size.They also can be various shapes, such as bar-shaped, star, cylinder, spherical or fault block.These oxide carriers many are commercially available, and their use simplifies the preparation of carbon monoxide-olefin polymeric of the present invention, but this is not necessary condition of the present invention.
In the embodiment of load, titanium and vanadium component can respectively or together be loaded on carrier.Preferred technology be by the ammonium vanadate of aequum and oxalic acid or lactic acid dissolution in the aqueous solution of TBALDH.If needed, this solution can be diluted, then for using just wet impregnation technology oxide impregnation thing carrier.Subsequently that the carrier of dipping is dry at about 110 DEG C.The material obtained may comprise the homogeneous dispersion of two kinds of metals, because drying solution creates uniform glass at 110 DEG C.The phosphide aqueous impregnation of the carrier aequum of the drying of vanadium and titanium will be comprised subsequently.
The order of dipping is not crucial usually.Excellent result can be obtained with phosphorus dipping after drying subsequently as described above by by vanadium and titanium total immersion stain.
Use just wet impregnation technology also can obtain excellent result for all dippings.If need higher useful load, can use than more solution, the then evaporating solvent needed for impregnation of just wetting.If needed, solution can be applied to the perimeter of oxide carrier.
After vanadium, titanium and phosphorus component being applied to carrier, can by catalyst in such as about 450 DEG C of calcinings.
Ternary V-Ti-P carbon monoxide-olefin polymeric disclosed herein is mainly unbodied, as determined in analyzed by X-ray diffraction.Interestingly, when using the aqueous formaldehyde charging of 55wt%, such as produce acrylic acid, although two kinds of catalyst are all amorphous materialses with V-Ti-P material prepared by V-Ti-P carbon monoxide-olefin polymeric ratio titanium tetrachloride of the present invention prepared by TBALDH with remarkable higher productive rate (>20%).This result shows that the micro-structural of catalyst of the present invention or uniformity have obviously different compared with prior art catalyst.
Except higher productive rate, the titanium of water soluble source is used to provide some advantage relative to use titanium chloride.Such as, can avoid the formation of gaseous hydrochloric acid, discontinuous titanium (IV) precursor is solute in water instead of troublesome out-phase gel; And the V-Ti-P catalyst obtained is formed with specific area higher inherently.
The appearance that the titanium compound such as TBALDH of water soluble forms the tendency of active V-Ti-P catalyst is beat all, because TiCl 4outside titanium source be proved to be and produced the poor catalyst prepared for acrylic acid.See, such as M.Ai, applied Catalysis, Vol.48,51-61 page (1989).Such as, when titanium dioxide is used as titanium precursor, the material obtained can not produce acrylic acid by formaldehyde and acetic acid.TiO was reported in other place 2can be formed prepare for acrylate catalytically-active materials (M.Abon etc., j. Catalysis, Vol.156,28-36 page (1995)), but this result can not be reproduced.
When using TBALDH, in catalyst synthesis, no longer require that the fact of exogenous lactate is also beyond thought.When saving lactic acid from the catalyst preparing relating to titanium tetrachloride, the material obtained is highly crystalline, and as determined by x-ray diffraction, but this material is relatively sluggish for acrylic acid synthesis.But, be such as unbodied and have more activity and selectivity significantly not existing under lactic acid with V-Ti-P material prepared by TBALDH.It is attracting for saving interpolation lactic acid, because it makes the number of steps in catalyst synthesis minimize and cause less organic material that must burn in air calcination.
In the 3rd, the invention provides preparation 2,3-unsaturated carboxylic acid, the method for such as acrylic or methacrylic acid.When mentioning " carboxylic acid " within a context, comprise corresponding carboxylate, such as acrylate and methacrylate.
Method of the present invention makes methyl alcohol source contact to obtain 2,3-unsaturated carboxylic acid with carboxylic acid under vapour phase condensation condition under being included in the existence of condensation catalyst.Described condensation catalyst comprises the mixed oxide of vanadium (V), titanium (Ti) and phosphorus (P).The titanium component of described condensation catalyst derived from water soluble as described herein, the organic titanic compound of redox active.
2,3-unsaturated carboxylic acid can with good productive rate, conversion ratio and selective preparation." productive rate " refers to (molal quantity of product)/(molal quantity of the reactant of charging) * 100.Such as, be (acrylic acid molal quantity)/(molal quantity of formaldehyde charging) * 100 by formaldehyde system acrylic acid productive rate %.Conversion ratio refers to (molal quantity of the molal quantity-unreacted reactant of the reactant of charging)/(molal quantity of the reactant of charging) * 100.Such as, the conversion ratio % of formaldehyde is (molal quantity-unreacted formaldehyde molal quantity of the formaldehyde of charging)/(molal quantity of the formaldehyde of charging) * 100.Selectively refer to (molal quantity of product)/(molal quantity * 100 of the molal quantity-unreacted reactant of feed reactants.Such as, formaldehyde is (acrylic acid molal quantity)/(molal quantity of the molal quantity-unreacted formaldehyde of the formaldehyde of charging) * 100 to acrylic acid selective %.Those skilled in the art will know that productive rate also equals conversion ratio and is multiplied by selective.When comparing embodiment, such as Embodiment B have 80% formaldehyde conversion and Embodiment C have 60% formaldehyde conversion, then think high by 20% than Embodiment C of the formaldehyde conversion of Embodiment B.In other words, it is poor by the mathematics of an embodiment on another percentage simply for comparing.
Be not particularly limited for formaldehyde source of the present invention.It can be anhydrous formaldehyde itself, 1,3,5-trioxane (being sometimes called simply herein " trioxane "), dimethoxymethane or diethyl acyl-oxygen methane.Or formaldehyde source can be the aqueous solution of formaldehyde.Formalin such as can comprise the formaldehyde of 30-65wt%.The example of these solution comprises the aqueous formaldehyde (formaldehyde of 55wt%) of formalin (formaldehyde of 37wt%) and technical grade.Described formalin can by the oxidation of methyl alcohol or by by water and trioxane such as with the blended commercial acquisition of the mol ratio of about 4:1.
Described carboxylic acid should have at least two hydrogen atoms on the α position of hydroxy-acid group.Described carboxylic acid preferably has the aliphatic carboxylic acid of 2-4 carbon atom.Preferred carboxylic acid is acetic acid and propionic acid.Most preferred carboxylic acid is acetic acid.When needs formation 2,3-esters of unsaturated carboxylic acids, term " carboxylic acid " comprises corresponding carboxylate within a context.The example of these carboxylates comprises acetic acid esters and propionic ester.
The description to carbon monoxide-olefin polymeric and the method for the preparation of this carbon monoxide-olefin polymeric above, such as vanadium, titanium, phosphorus and alkali metal compound, catalyst Formula, alkali metal, preformed carrier, water are removed to the description of step and difunctional compound, also the method for preparation 2,3-unsaturated carboxylic acid is applicable to.
The mol ratio of formaldehyde components and carboxyl acid component can be 0.1-10, preferred 0.2-5 and more preferably 0.2-2.The mol ratio of water and formaldehyde components can be 0-5, preferred 0-3 and more preferably 0-1.5.
The method can operate at the temperature of 200-400 DEG C, preferred 225-375 DEG C, and more preferably 275-375 DEG C.
The method can be run under 0.1-10 clings to the pressure of absolute pressure (bara), preferred 0.5-5 bar and more preferably 1-1.5 bar.
In some embodiment of method of the present invention, liquid feed rate can be 1.0-1000mL/kg catalyst per minute, preferred 10-100mL/kg catalyst per minute.
In other embodiment of method of the present invention, reactant can with oxygen and inert carrier gas, the air of such as nitrogen or oxygen depletion, is fed in condensation reactor together.The gas from the method recirculation can be used.Inert composition can exist with the concentration of the 0-90mol% of combined feed, preferred 25-85mol%, and more preferably 30-80mol%.The concentration of oxygen components can be 0.5-6mol%, preferred 2-5mol%, and more preferably 3-4mol%.Low-level oxygen allows coke to accumulate on a catalyst.On the other hand, high-caliber oxygen can cause the overfire of reactant and product.
In the embodiment that oxygen is co-fed, air speed should preferably 50-400mol charging/(kg catalyst-hour), more preferably 100-300mol charging/(kg catalyst-hour), and most preferably 125-200mol charging/(kg catalyst-hour).Term " mol charging " is intended to comprise all substances being fed to catalyst, comprises organic matter, water, oxygen and inert material.These embodiments of the present invention make use of the oxygen of the appropriate level of charging, water and the effect of the combination of air speed that provides to improve speed and selective and affect productive rate indistinctively.When air speed is too low, the result of the mainly formaldehyde destruction of any difference on formaldehyde conversion.When suppressing coke to be formed, catalyst can regeneration between reaction runs in atmosphere at such as 400 DEG C.
Usually, the air speed improving reactant can improve reaction rate, but this is usually along with the corresponding reduction on productive rate and conversion ratio.Be surprised to find that when air speed improves, in fact some condition of this method can allow improve speed and do not reduce productive rate.
Inhibitor (such as hydroquinones) can be added in 2,3-unsaturated carboxylic acid product to minimize polymerization.
the list of unrestricted embodiment
Embodiment A is the carbon monoxide-olefin polymeric of the mixed oxide comprising vanadium (V), titanium (Ti) and phosphorus (P), wherein titanium component derived from water soluble, the organic titanic compound of redox active.
The carbon monoxide-olefin polymeric of embodiment A, it has general formula VTi ap bo c, wherein a is the number of 0.3-6.0, and b is the number of 2.0-13.0 and c is the atomicity needed for chemical valence meeting V, Ti and P, or wherein a is 1.0-4.0 and b is 4.0-10.0.
Embodiment A or there is the carbon monoxide-olefin polymeric of embodiment A of one or more intervention feature, wherein said organic titanic compound comprise two (2 hydroxy propanoic acid) two hydroxide two ammonium close titanium (IV).
Embodiment A or have the carbon monoxide-olefin polymeric of embodiment A of one or more intervention feature, it comprises preformed carrier further.
Embodiment A or have the carbon monoxide-olefin polymeric of embodiment A of one or more intervention feature, it comprises preformed carrier further, and wherein preformed carrier comprises silica, aluminium oxide, titanium oxide, Titanium pyrophosphate, zirconia or zirconium pyrophosphate.
Embodiment A or have the carbon monoxide-olefin polymeric of embodiment A of one or more intervention feature, it comprises preformed carrier further, and wherein preformed carrier has the particle diameter of 0.1mm-20mm.
Embodiment B is the method that preparation comprises the carbon monoxide-olefin polymeric of the mixed oxide of vanadium (V), titanium (Ti) and phosphorus (P).The method comprises the following steps:
(a) providing package containing water soluble, the aqueous solution of the organic titanic compound of redox active;
B vfanadium compound and phosphorus compound join in the aqueous solution of this titanium to form the mixture of catalytic component by ();
C () heats this mixture;
D () removes water to obtain the solid residue comprising described catalytic component from heat-treated mixture; With
E () calcines this solid residue in the presence of air at elevated temperatures to obtain carbon monoxide-olefin polymeric.
The method of embodiment B, wherein water remove step (d) comprise distillation or evaporation.
The method of embodiment B, wherein water removes step (d) and comprises and anti-solvent to be joined in this mixture to be settled out catalytic component and to isolate precipitation to obtain solid residue from liquid.
The method of embodiment B, wherein water removes step (d) and comprises and anti-solvent to be joined to be settled out catalytic component and to isolate precipitation to obtain solid residue from liquid in this mixture, and wherein by filtering precipitation and separation from liquid.
The method of embodiment B, wherein water removes step (d) and comprises and anti-solvent to be joined in mixture to be settled out catalytic component and to isolate precipitation to obtain solid residue from liquid, wherein by filtering precipitation and separation from liquid, and wherein said anti-solvent is the polar compound being selected from alcohol, ketone, aldehyde, ether and ester, or described anti-solvent is alcohol.
Embodiment B or have the method for embodiment B of one or more intervention feature, wherein carbon monoxide-olefin polymeric has general formula VTi ap bo c, wherein a is the number of 0.3-6.0, and b is the number of 2.0-13.0, and c is the atomicity needed for chemical valence meeting V, Ti and P; Or wherein a is 1.0-4.0, and b is 4.0-10.0.
Embodiment B or there is the method for embodiment B of one or more intervention feature, wherein said organic titanic compound comprise two (2 hydroxy propanoic acid) two hydroxide two ammonium close titanium (IV).
Embodiment B or have the method for embodiment B of one or more intervention feature, wherein said carbon monoxide-olefin polymeric comprises preformed carrier further.
Embodiment B or have the method for embodiment B of one or more intervention feature, it comprises preformed carrier further, and wherein preformed carrier comprises silica, aluminium oxide, titanium oxide, Titanium pyrophosphate, zirconia or zirconium pyrophosphate.
Embodiment B or have the method for embodiment B of one or more intervention feature, it comprises preformed carrier further, and wherein preformed carrier has the particle diameter of 0.1mm-20mm.
Embodiment B or there is the method for embodiment B of one or more intervention feature, wherein carbon monoxide-olefin polymeric comprises preformed carrier further, and is wherein joined in the mixture of catalytic component by preformed carrier before heat treatment step (c).
Embodiment B or there is the method for embodiment B of one or more intervention feature, difunctional compound joins in the mixture of catalytic component before being included in heat treatment step (c) further by it, and wherein said difunctional compound comprises citric acid, lactic acid, glycolic, oxalic acid, ethylene glycol, butanediol, pentanediol or hexylene glycol; Or wherein said difunctional compound comprises lactic acid.
Embodiment C is the method for preparation 2,3-unsaturated carboxylic acid.The method makes formaldehyde source contact with carboxylic acid to obtain 2,3-unsaturated carboxylic acid under vapour phase condensation condition under being included in the existence of condensation catalyst.Condensation catalyst comprises the mixed oxide of vanadium (V), titanium (Ti) and phosphorus (P).The titanium component of condensation catalyst derived from water soluble, the organic titanic compound of redox active.
The method of embodiment C, wherein formaldehyde source comprises formaldehyde, 1,3,5-trioxane, dimethoxymethane or diethyl acyl-oxygen methane, and carboxylic acid comprises acetic acid or propionic acid.
Embodiment C or have the method for embodiment C of one or more intervention feature, wherein formaldehyde source comprises the aqueous solution of formaldehyde, 1,3,5-trioxane, dimethoxymethane or diethyl acyl-oxygen methane, and carboxylic acid comprises acetic acid or propionic acid.
Embodiment C or there is the method for embodiment C of one or more intervention feature, wherein formaldehyde source comprises formaldehyde, 1,3, the aqueous solution of 5-trioxane, dimethoxymethane or diethyl acyl-oxygen methane, and carboxylic acid comprises acetic acid or propionic acid, and the wherein said aqueous solution comprises the formaldehyde of 30-65wt%.
Embodiment C or there is the method for embodiment C of one or more intervention feature, wherein said organic titanic compound comprise two (2 hydroxy propanoic acid) two hydroxide two ammonium close titanium (IV).
Embodiment C or have the method for embodiment C of one or more intervention feature, wherein said carbon monoxide-olefin polymeric comprises preformed carrier further.
Embodiment C or have the method for embodiment C of one or more intervention feature, it comprises preformed carrier further, and wherein said preformed carrier comprises silica, aluminium oxide, titanium oxide, Titanium pyrophosphate, zirconia or zirconium pyrophosphate.
Embodiment C or have the method for embodiment C of one or more intervention feature, it comprises preformed carrier further, and wherein said preformed carrier has the particle diameter of 0.1mm-20mm.
Embodiment C or there is the method for embodiment C of one or more intervention feature, wherein condensation condition comprises the combined feed air speed of 50-400mol charging/(kg catalyst hour), or combined feed air speed is 100-300mol charging/(kg catalyst hour); Or combined feed air speed is 125-200mol charging/(kg catalyst hour).
The present invention can illustrate further by following examples, but is to be understood that these embodiments are only for purpose of explanation, are not intended to limit the scope of the invention.Except as otherwise noted or context have different hint, all percentage is percetage by weight.
Embodiment
material
D/L-lactic acid (90wt%), ammonium metavanadate (99+wt%NH 4vO 3), phosphoric acid (85wt%H 3pO 4), two (2 hydroxy propanoic acid) two hydroxide two ammonium close titanium (IV) (aqueous solution of 50wt%), titanium tetrachloride (>=99wt%TiCl 4), and the titanium dioxide colloidal suspension (23.38wt%TiO in water 2) from suppliers buy and in statu quo use.
abbreviation
XRD=powder x-ray diffraction, XRF=X-ray fluorescence spectra, TPD=temperature programmed desorption, SCCM=sccm clock; MeOAc=methyl acetate, MeOH=methyl alcohol, MA=methyl acrylate, H2CO=formaldehyde, HOAc=acetic acid, HOPr=propionic acid, mmol=mM, prod=product, AA=acrylic acid, two (trimethyl silyl) trifluoroacetamide of BSTFA=N, O-, TMSCI=tri-methyl-chlorosilane.
xRD measures
The RigakuMiniflexX-Ray Diffraction Spectroscopy instrument of the copper anode X-ray tube of all XRD measurements all under use is operated in 30kV and 15mA carries out.Diffraction patterns are collected at the 2 θ angles spent by the 2 θ angles to 75 of 5 degree, and sampling width is 0.02 degree and sweep speed is 1.00 degree/min.
Crystallite dimension based on the full width at half maximum (FWHM) (fullwidthhalfmaximumforpeaks) at the peak in diffraction pattern measurement and use Scherrer equation (P.N.Scherrer, ges. Wiss. Gottingen, Math.-Phys. Kl. 2, 96-100 (1918)) calculate.Use based on Rietveld method the facies analysis of thinning algorithm calculation in quantity (H.M.Rietveld, j. Applied Crystallography 21, 86-91 (1988)).Crystallinity percentage calculates based on the integrated intensity from independent diffraction pattern, and the peak being greater than the crystallite dimension of 30 is defined as crystal, the peak being less than or equal to the crystallite dimension of 30 be defined as amorphous (N.S.Murthy etc., polymers 31, 996-1002 (1990)).
desorption by heating is measured
The mass spectrum being connected to MicrometricsAutochemII2920 analyzer exit is used to carry out TPD mensuration.Isopropyl alcohol is used to carry out as the total acidity of molecular detection and being determined as follows of total alkalinity.The sample of about 0.05g is weighed into the quartzy U-shaped pipe being placed in ceramics furnace.Make sample stand program temperature circulation, it, by comprising the helium of 10% oxygen down to the heat cycles of 450 DEG C, forms to the cooling steps of 40 DEG C.Use the steam generator of MicromeriticsAutochem2920 analyzer that isopropyl alcohol is added sample.Described steam generator is operated by the flask comprising isopropyl alcohol by room temperature bubbling helium." steam-saturated " helium obtained is conveyed through the sample loop of heating and is injected on sample.After the surface soaking into sample, make dry helium through sample to remove the steam of any physical absorption.Subsequently flowing He stream in 20 DEG C/min be finally heated to ~ 450 DEG C, by the gas collection mass spectrometric data flowing through sample within this time.
gas chromatographic measurement
At Measuring Time section adduction liquid collecting body Product samples, weigh and analyzed by gas-chromatography.Sample is weighed into the weight (wherein X is the actual numerical value shown on balance) to the record of 0.1XXX in gas-chromatography (GC) bottle.Use LEAP unit automatically to add 200 μ L internal standard compounds (the 0.7325g dodecane in 100mL pyrimidine) subsequently, add the BSTFA (w/TMSCl) of 1.0mL subsequently.Subsequently bottle is placed in heating plate upper 30 minute of 80 DEG C.In order to be separated all components, each sample is infused in two posts run parallel that same instrument (has the Shimadzu2010 gas chromatograph of AOC-20 Autosampler).Gas chromatographic measurement to be used to quantize in product liquid all components in addition to formaldehyde.
liquid chromatogram is measured
The quantification of the formaldehyde in product liquid stands at 80 DEG C, 25%v/vH at reactant mixture sample 2sO 4after acid hydrolysis in the aqueous solution 30 minutes, high performance liquid chromatography is used to carry out.Make acid hydrolysis products and dinitrophenylhydrazine reaction, then use PhenomenexLunaC8 post to adopt the water of 1:1: acetonitrile mobile phase is analyzed under degree of grade (isocratic) condition.The separation and detection of the DNPH derivative of formaldehyde uses the Agilent1100HPLC system had at the UV-Vis detector of 360nm monitoring to carry out.Concentration of formaldehyde in product liquid is based on the calibrated and calculated using the external standard prepared by formalin.The quantification of the formaldehyde in liquid charging moves rate calculations based on the ratio of water and trioxane and liquid feed stream.
embodiment 1
prepare amorphous V-Ti-P catalyst by method A and use the reactor of anhydrous liquid charging to screen
1. V (IV) H 3 pO 4 the preparation of solution
In 500mL single necked round bottom flask, ammonium metavanadate (9.75g) cream-coloured for orange is suspended in the lactic acid of 50mL and the deionized water of 200mL., within the time of 15 minutes, the orthophosphoric acid (52.5g) of 85% is joined in the blue vanadium solution of clarification to obtain glaucous solution at 70 DEG C after 1 hour 70 DEG C of heating.With the water of minimum, residual reactants is washed in reaction flask.
2. the preparation of V-Ti-P catalyst
By 50wt% two (2 hydroxy propanoic acid) two hydroxide two ammonium close titanium (IV) solution (109.19g) and join and be equipped with in 1-L tri-mouthfuls of tank reactors of condenser and mechanical agitator.V/P solution from above step 1 is poured in Ti solution lentamente to obtain blue suspension.Rinse V/P flask with the water of 30mL and content is joined in reaction flask.Subsequently by mixture 130 DEG C, stir under 700-800rpm 16 hours blue to glaucous suspension to obtain.Then remove water by distillation 4-6 hour (being set in the oil bath of 130 DEG C), and the light green solid of the humidity obtained to be transferred on ceramic disk and to heat 16 hours at 300 DEG C in atmosphere in Muffle furnace.Afterwards, the solid obtained pulverized and divided by 8 × 14 mesh sieves.Subsequently the material of this 8x14 sieve mesh is calcined in quartz tube furnace at 450 DEG C 6 hours in atmosphere to obtain the erose granule of light green color.Surface property and total composition of the catalyst prepared in this embodiment are summarised in table 1.
3. acrylic acid preparation
Have the trioxane charging of mol ratio 12 acetic acid/1 vapour phase condensation experiment at 325 DEG C, the charging of 0.083mL liquid/minute and 80SCCMN 2under carry out three hours.The performance of catalyst is summarized in table 3.In table 3, term " product, g " refers to the quality of the product liquid of recovery.Term " reactant of charging, g " only comprises those reactants be fed to as liquid in reactor: trioxane and acetic acid.
The condensation reaction of acetic acid and trioxane (formaldehyde source) is at length=61cm(24 inch) 25-mm overall diameter (21mm interior diameter) quartz reactor tube in carry out.The heat of reactor is provided by BarnsteadInternational electric tube furnace (model F21100).Collect product liquid being assembled in the there-necked flask on water-cooled condenser, described water-cooled condenser is connected to the dry-ice condenser with trap (trap).3rd mouth of flask is equipped with stopper, and it allows to add a small amount of hydroquinones inhibitor crystal.Starting to add hydroquinones crystal when collecting each sample.The bottom of recipient flask is equipped with switch to allow to discharge product liquid.
Quartz reactor is upwards 20cm(8 inch in the bottom from pipe) there is indentation.The impressed reactor area of tool is placed in the bottom of the bringing-up section close to stove.Reactor is also equipped with thermocouple sheath, and it extends to below indentation about 1 inch by the top of reactor.First this reactor loads the height of more than quartz plate to indentation about 2.5 inches with the centre making catalyst be positioned at stove.Subsequently to the catalyst charge loading 5.0g in reactor.Thermocouple in thermocouple sheath is placed on the immediate vicinity of catalyst bed.Enough quartz plates (about 2.5 inches) are added to reach the top of stove heating region to region more than catalyst charge.The performance of this catalyst gathers in table 3.
This embodiment shows that TBALDH compound is the suitable precursor of the active V-Ti-P material of synthesis catalytic, under standard screening conditions, provide acrylic acid with good productive rate and high-purity.Mole composition of catalyst is almost identical with the catalyst used in following comparative example 1, but compared with the catalyst of embodiment 1, the catalyst in comparative example 1 only has the surface area of 60%.The catalyst of embodiment 1 is compared with the catalyst of comparative example 1, and total acidic center is higher; Be respectively 92.5(μm of ol/g) contrast 64.2(μm of ol/g).The powder x-ray diffraction analysis of catalyst shows its mainly unbodied (Fig. 1).
comparative example 1
prepare amorphous V-Ti-P catalyst by method B and use the reactor of anhydrous liquid charging to screen
Catalyst in this embodiment according at M.Ai, applied Catalysis, Vol.48, the method described in 51-61 page (1989) and JP1989-068335A preparation.
1. Ti (OH) 4 the preparation of gel
The water-ice of 300mL and the deionized water of 300mL is loaded to 5L tri-mouthfuls of round-bottomed flasks.Described flask is furnished with the charging hopper of 125mL and is expelled to saturated sodium bicarbonate aqueous solution.Add lentamente subsequently in titanium tetrachloride (34.6g) to intensively stirred water/ice mixture.With air stream, reactor atmosphere is poured in wash solution to remove gaseous state HCl.The pH of the colourless solution obtained between zero and one.
Once solution is heated to room temperature, just dilutes by the deionized water of 2.5L and by the ammonium hydroxide adding 200mL5.0M, pH be adjusted between 10 and 11.Define pale white solid immediately.Its air oxygen detrition, with the water washing of 2 × 1L to obtain the pasty mass block of white, is up to 5 hours to obtain having the white material of the denseness of similar gels by this filtration of material.
2. V (IV) H 3 pO 4 the preparation of solution
The program following embodiment 1 step 1 prepares V/P solution.
3. the preparation of V-Ti-P catalyst
In the 1-L tri-mouthfuls of tank reactors being equipped with condenser, the hydroxide gel from above step 1 to be suspended in the water of 200mL and under 700-800rpm the mechanical agitation sufficiently long time to obtain uniform white suspension.V/P solution from above step 2 is poured in this gel suspension lentamente to obtain blue suspension.Rinse V/P flask with 50ml water and content is added in reaction flask.Subsequently by mixture 130 DEG C, stir under 700-800rpm 16 hours blue to glaucous suspension to obtain.
Then remove water by distillation 6 hours (being set in the oil bath of 130 DEG C), and the light green solid of the humidity obtained to be transferred on ceramic disk and to heat 16 hours at 300 DEG C in atmosphere in Muffle furnace.Afterwards, the solid obtained pulverized and divided by 8 × 14 mesh sieves.Subsequently by the material of this 8x14 sieve mesh in quartz tube furnace in atmosphere (60SCCM) at 450 DEG C, calcine 6 hours to obtain the erose granule of light green color.Surface property and total composition of the catalyst prepared in this embodiment gather in Table 1.The powder x-ray diffraction analysis of catalyst shows its mainly unbodied (Fig. 2).
4. acrylic acid preparation
The condensation reaction of acetic acid and trioxane (formaldehyde source) carrying out like that as described in Example 1, is only the use of and has length=107cm(42 inch in this embodiment) the quartz reactor tube of 25mm overall diameter (21mm interior diameter).By having 61cm(24 inch) the Lindberg3-unit electric furnace of long heating region provides the heat of reactor.Collect product liquid being assembled in the there-necked flask on water-cooled condenser, described water-cooled condenser is connected to the dry-ice condenser with trap (trap).3rd mouth of flask is equipped with stopper, and it allows to add a small amount of hydroquinones inhibitor crystal.Starting to add hydroquinones crystal when collecting each sample.The bottom of recipient flask is equipped with switch to allow to discharge product liquid.At Measuring Time section adduction collection fluid sample, weigh and analyzed by gas-chromatography.
Quartz reactor is upwards 30.5cm(12 inch in the bottom from pipe) there is indentation.The impressed reactor area of tool is placed in the bottom of the bringing-up section close to stove.Reactor is also equipped with thermocouple sheath, and it extends to below indentation about 1 inch by the top of reactor.First this reactor loads the height of more than quartz plate to indentation about 10 inches with the centre making catalyst be positioned at 3-unit stove.Subsequently to the catalyst charge loading 5.0g in reactor.Thermocouple in thermocouple sheath is placed on upwards 1.5 inches, the bottom from catalyst bed.Enough quartz plates are added to reach the top of three-first stove heating region to region more than catalyst charge.The performance of this catalyst gathers in table 3.
This embodiment proof is reproducible according to the preparation method of prior art and the catalyst obtained shows similar to the catalyst of the present invention described in embodiment 1.Under an inert atmosphere and use anhydrous liquid charging, two kinds of catalyst all prepare acrylic acid with good productive rate.Acetic acid accountability (accountability) is almost identical in both cases.Two kinds of catalyst are also all unbodied and have similar total composition.Although there is the similitude on these surfaces, the micro-structural of the catalyst in this embodiment and embodiment 1 has remarkable difference, as by the contrast in surface area and acidity measurement confirm.
comparative example 2
by the crystal-amorphous V-Ti-P catalyst of method C preparation mixing and the reactor screening of use anhydrous liquid charging
1. V (IV) H 3 pO 4 the preparation of solution
The program following embodiment 1 step 1 prepares V/P solution.
2. the preparation of V-Ti-P catalyst
The titanium dioxide colloidal dispersion (41.3g) of 23.38wt% and the deionized water of 100mL are joined and is equipped with in 1L tri-mouthfuls of tank reactors of condenser and mechanical agitator.V/P solution from above step 1 is poured in suspension lentamente to obtain blue suspension.Rinse V/P flask with 25ml water and content is added in reaction flask.Subsequently by mixture 130 DEG C, stir 16 hours under 700-800rpm to obtain glaucous suspension.Then remove water by distillation 6 hours (being set in the oil bath of 130 DEG C), and the light green solid of the humidity obtained to be transferred on ceramic disk and to heat 16 hours at 300 DEG C in atmosphere in Muffle furnace.Afterwards, the solid obtained pulverized and divided by 8 × 14 mesh sieves.Subsequently the material of this 8x14 sieve mesh is calcined in quartz tube furnace in air (60SCCM) at 450 DEG C 6 hours to obtain the erose granule of lead.Surface property and total composition of the catalyst prepared in this embodiment gather in Table 1.Vapour phase condensation experiment and product analysis carry out as described in example 1 above.The performance of catalyst gathers in table 3.
This embodiment shows that titanium dioxide is the precursor of the instability of preparation catalytic activity V-Ti-P catalyst.Particularly, relative to vanadium, BET surface area is relatively low, and total acidic center and total mol composition are also.This material can not produce acrylic acid by formaldehyde and acetic acid.The powder x-ray diffraction analysis of catalyst shows unknown amorphous materials and the mixture of crystallization rutile.
comparative example 3
crystallization VO (HPO is prepared by method D 4 ) (H 2 o) 0.5 the reactor screening of catalyst and the charging of use anhydrous liquid
Catalyst in this embodiment according at .K.Bartley etc., " VanadiumPhosphateCatalysts " metal Oxide Catalysis, the step preparation that 499-537 page (S.D.Jackson & J.S.JHargreaveseds.2009) describes.
The isobutyl alcohol of 100.08g vanadium pentoxide and 600mL is added all in a nitrogen atmosphere in the 1L tank reactor being equipped with mechanical agitator, condenser and charging hopper.Heat (being set in the oil bath of 130 DEG C) content 1 hour under reflux, slowly add the phosphoric acid of 139.44g85% subsequently, and under reflux reaction temperature is kept 22 hours.The sky blue suspension obtained comprises the insoluble material of a small amount of dark color.The phosphoric acid of other 5.53g85% is added subsequently together with other 150mL isobutanol.Continue other 7 hours of backflow subsequently.After cooling to room temperature, blue suspension is poured into the Buchner funnel that filter paper is housed; Heavier insoluble impurity is retained in reaction flask.Subsequently by isolated by vacuum filtration blue solid and with the ethanol of 200mL washing and at room temperature dry while vacuumizing.Water-soluble impurity is removed to reflux to spend the night by heating the suspension of blue solid in water in a nitrogen atmosphere.Then filter when mixture remains heat, filter paper stays blue solid and leave yellow filtrate in filter flask.Then by blue solid at 110 DEG C in atmosphere dry 22 hours to obtain blue-green cake.Afterwards, this material disintegrating is divided by 8 × 14 mesh sieves.The XRD analysis (Fig. 4) of this material shows the VO (HPO that it is crystallization 4) (H 2o) 0.5.Surface property and total composition of the catalyst prepared in this embodiment gather in Table 1.Vapour phase condensation experiment is carried out according to the description in embodiment 1.The performance of catalyst gathers in table 4.
This embodiment prove the catalyst prepared by method D prepare on acrylic acid not as the V-Ti-P catalyst of the present invention in embodiment 1 or the V-Ti-P catalyst in comparative example 1 effective.As described in XRD pattern, the surface of this catalyst is made up of half hypophosphite monohydrate hydrogen-oxygen vanadium (vanadylhydrogenphosphatehemihydrate) of crystallization.This discrete mass is not observed from the similar XRD analysis of the amorphous catalyst described in embodiment 1 or comparative example 1.
comparative example 4
prepared by method E (VO) of crystallization 2 (P 2 o 7 ) catalyst and use the reactor screening of anhydrous liquid charging
Catalyst in this embodiment according at M.Abon etc., j. Catalysis, the step preparation described in Vol.156, pp.28-36 (1995).
The 8x14-order VO (HPO that about 46g is prepared in comparative example 3 4) (H 2o) 0.5flow down at 100SCCM nitrogen and heat 47 hours to obtain 37.91g light brown particle in 500 DEG C.The XRD analysis (Fig. 5) of this material shows the Vanadyl pyrophosphate (VO) that it is crystallization 2(P 2o 7).Surface property and total composition of the catalyst prepared in this embodiment gather in Table 1.Vapour phase condensation experiment is carried out according to the description in embodiment 1.The performance of catalyst gathers in table 4.
This embodiment prove this catalyst prepare on acrylic acid not as the V-Ti-P catalyst of the present invention in embodiment 1 or the V-Ti-P catalyst in comparative example 1 effective.As described in XRD pattern, the surface of this catalyst is made up of the Vanadyl pyrophosphate of crystallization.This discrete mass is not observed from the similar XRD analysis of the amorphous catalyst described in embodiment 1 or comparative example 1.
comparative example 5
prepare the V-Ti-P-Mo catalyst of crystallization by method F and use the reactor screening of liquid, aqueous charging
Except graphite not being added to except in catalyst, according to the step Kaolinite Preparation of Catalyst described in C.D.Rodica etc., RO114084B1 (1999).
By vanadium oxide (V) (3.9g) and titanium dioxide (6.65g), molybdenum oxide (0.45g) and 85% phosphoric acid (17mL) mix to obtain dense and burned in ceramic disk.Then by this material 200 DEG C in Muffle furnace air oxygen detrition 3 hours to obtain hard yellow solid.Afterwards, this solid pulverized and divided by 8 × 14 mesh sieves.Then by the particle of this screening in Muffle furnace at 300 DEG C air calcination 2 hours.The XRD analysis (Fig. 6) of this material shows the titanium dioxide that it is crystallization; Do not observe vanadium and phosphorus component.Surface property and total composition of the catalyst prepared in this embodiment gather in Table 1.
Except being arranged in except those described in RO114084B1 by reaction condition, vapour phase condensation experiment is carried out as described in comparative example 1.Furnace temperature is set to 350 DEG C, and liquid feed rate is set to 0.025mL/ minute, and nitrogen stream is set to 51SCCM.Charging is made up of the mixture of the 4:0.67:9 mol ratio of acetic acid, trioxane and water; Running time is 360 minutes.The performance of catalyst gathers in table 4.
This embodiment attempts reproducing result disclosed in RO114084B1, and it has claimed the acrylic acid yield of 86.3%.But, it is found that acrylic acid actual yield is less than 1%.This result, combined catalyst comprises crystallization TiO 2discovery, for following opinion provides support: titanium dioxide prepares the unaccommodated precursor of active formaldehyde alkanoic acid condensation catalyst.
embodiment 2
prepare amorphous V-Ti-P catalyst by method G and use the reactor of liquid, aqueous charging to screen
Catalyst in this embodiment first by the 1L tri-mouthfuls of tank reactors being equipped with still head and mechanical agitator, ammonium metavanadate (19.54g) is suspended in 218.41g50wt% two (2 hydroxy propanoic acid) two hydroxide two ammonium close in titanium (IV) solution and then add the preparation of 200mL deionized water.At room temperature under 700rpm, stir beige coloured suspension 10 minutes, then add the phosphoric acid of 105.57g85%, rinse with the water of about 50mL afterwards.Color becomes faint yellow and mixture retrogradation immediately, then becomes green and in 20 minutes, becomes light green color again.Then suspension added hot reflux (being set in the oil bath of 130 DEG C) and in three hours, pass through the water that 220mL is collected in distillation.After cooling to room-temperature, the light green color semisolid obtained to be scraped in ceramic disk and in Muffle furnace in 300 DEG C of air calcination 16 hours to obtain blackish green solid, it is divided by 8 × 14 mesh sieves.Then the granule of this 8x14 sieve mesh is calcined 6 hours to obtain light green color granule at 450 DEG C in quartz tube furnace in the air stream of 60SCCM.The XRD analysis (Fig. 7) of this material shows that it is mainly unbodied.Surface property and total composition of the catalyst prepared in this embodiment gather in Table 1.
Except 325 DEG C, the liquid charging of 0.089mL/minute under employ the liquid charging be made up of 12 trioxane/4.09, acetic acid/1 water mol ratios, be arranged on outside 70SCCM with carrier gas (nitrogen), the condensation reaction of acetic acid and trioxane (formaldehyde source) carrying out like that as described in claim 1 in this embodiment.The performance of catalyst gathers in table 5.
This embodiment proves that (a) uses the TBALDH of water soluble to allow catalyst synthesis faster, because all three kinds of catalyst precarsors merge in one-step method, (b) TBALDH is used to create the active catalyst prepared for acrylic acid, even if do not use lactic acid in catalyst preparing as the titanium source of V-Ti-P material.Be unbodied by the known catalyst obtained of XRD and there is the surface area closely similar with the catalyst described in embodiment 1 and the total composition closely similar with the catalyst described in embodiment 1 and comparative example 1.
comparative example 6
prepare the V-Ti-P catalyst of crystallization by method H and use the reactor screening of anhydrous liquid charging
Except lactic acid is excluded except step, the step preparation of the catalyst in this embodiment described by comparative example 1.The XRD analysis (Fig. 8) of this material shows the mixture of vanadium (III) series-phosphate that it is crystallization and titanium diphosphate (titaniumdiphosphate).Surface property and total composition of the catalyst prepared in this embodiment gather in Table 1.Vapour phase condensation reaction carrying out like that as described in Example 1.The performance of catalyst gathers in performance table 5.
This embodiment proves, when using titanium tetrachloride as titanium precursor between catalyst synthesis phase and getting rid of lactic acid, to obtain the V-Ti-P material with Low acid and low surface area.The surface of the solid obtained is the mixture of crystalline compounds, and it shows the catalytic activity of going on business significantly for acrylic acid synthesis.Productive rate is less than 10%, and is selectively less than 12%.This embodiment further highlights the following fact: TBALDH is more attractive V-Ti-P precursor, because lactate group intrinsic in salt is enough to reduce vanadium between catalyst synthesis phase, it helps the surface area forming amorphous surfaces and produce increase after firing.
embodiment 3
use V-Ti-P catalyst (method A, with the 2X scale) life search of anhydrous liquid charging
Catalyst in this embodiment prepares (embodiment 1) by method A, but with the scale of twice.The condensation reaction of acetic acid and trioxane (formaldehyde source) carrying out like that as described in Example 1 in this embodiment, just at 325 DEG C, the charging of 0.083mL liquid/minute under employ the liquid charging that is made up of 12 acetic acid/1 trioxane mol ratios and carrier gas is nitrogen (49SCCM) and air (21SCCM).Reaction operation 27 hours.In addition, employ there is length=79cm(31 inch) the quartz reactor tube of 25mm overall diameter (21mm interior diameter).By having long 50cm(19.5 inch) the AppliedTestSystems series 3210 ternary electric furnaces of the thermal treatment zone heat of reactor is provided.Product liquid is collected in the there-necked flask being furnished with glycol-cooled (0 DEG C) chuck.3rd mouth of flask is connected to water-cooled condenser, and it is connected to dry ice trap.The end of receiver flask, is equipped with switch to allow to discharge product liquid.
Quartz reactor is upwards 13cm(5 inch in the bottom from pipe) there is indentation.The impressed reactor area of tool is placed in the bottom of the bringing-up section close to stove.Reactor is also equipped with thermocouple sheath, and it extends to below indentation about 1 inch by the top of reactor.First this reactor loads the height of more than quartz plate to indentation about 8 inches with the centre making catalyst be positioned at ternary stove.Then in reactor, load the catalyst charge of 5.0g.Thermocouple in thermocouple sheath is placed on 1.5 inches, more than the bottom of catalyst bed place.Enough quartz plates are added to reach the top of three-first stove heating region to region more than catalyst charge.
At Measuring Time section adduction collection fluid sample, weigh and analyzed by gas-chromatography and HPLC.The performance of catalyst gathers in table 6.
This embodiment shows the V-Ti-P catalyst of the present invention prepared with TBALDH within the time of 27 hours with medium productive rate with selectively obtain acrylic acid.The having of oxygen helps the catalyst life extended.As the result using anhydrous liquid charging, suspect that high coking rate causes the productive rate that in the end data point observes and reduces.
comparative example 7
use the life search of the V-Ti-P catalyst (method B, with 2X scale) of anhydrous liquid charging
Catalyst in this embodiment prepares (comparative example 1) by method B, but with the scale of twice.Vapour phase condensation experiment is carried out as in embodiment 3.The performance of catalyst gathers in table 7.
This embodiment proves that the V-Ti-P catalyst prepared according to prior art when adopting anhydrous liquid charging within 27 little periods shows similar to catalyst of the present invention.Again, the productive rate observed in the 3rd data point reduces owing to high coking rate.
embodiment 4
use the life search of the V-Ti-P catalyst (method A, with 2X scale) of liquid, aqueous charging
The catalyst used in this embodiment is identical catalyst charge used in embodiment 3, and just it regenerates by heating at 400 DEG C under the oxygen (94vol% nitrogen) of 6vol% after this embodiment for 16 hours.Then carrying out vapour phase condensation reaction according to embodiment 3, is at 325 DEG C respectively, the charging of 0.089mL liquid/minute under use the liquid charging be made up of 12 trioxane/4.09, acetic acid/1 water mol ratios.Carrier gas is nitrogen (49SCCM) and air (21SCCM).Reaction operation 27 hours.The performance of catalyst gathers in table 8.
This example demonstrates the V-Ti-P catalyst prepared with TBALDH and maintain (1) when using liquid, aqueous charging for acrylic acid very high selective moderate yield consistent with (2).Ultimate yield close to 55% is relatively higher than identical point in embodiment 3, and supposition is due to lower coking rate.
comparative example 8
use the life search of the V-Ti-P catalyst (method B, with 2X scale) of liquid, aqueous charging
The catalyst used in this embodiment is the identical catalyst charge used in comparative example 7, except it regenerates by heating at 400 DEG C under the oxygen (94vol% nitrogen) of 6vol% after this embodiment for 16 hours.Then carry out vapour phase condensation reaction according to embodiment 3, just at 325 DEG C, the charging of 0.089mL liquid/minute under use the liquid charging be made up of 12 trioxane/4.09, acetic acid/1 water mol ratios.Carrier gas is nitrogen (49SCCM) and air (21SCCM).Reaction operation 27 hours.The performance of catalyst gathers in table 9.
This embodiment proves that the V-Ti-P catalyst prepared according to prior art when using liquid, aqueous charging can not obtain acrylic acid with the productive rate that catalyst of the present invention is equally high.Even if for acrylic acid selective same height and to react the life-span also suitable, but methanol conversion is always lower more than 20% than what observe in embodiment 4.In view of two kinds of V-Ti-P catalyst all indicate similar activity and selectivity when using anhydrous liquid charging, this is astonishing.
embodiment 5
use anti-solvent to prepare amorphous V-Ti-P catalyst by method I and use the reactor screening of liquid, aqueous charging
The catalyst used in this embodiment first by the 1L tri-mouthfuls of tank reactors being equipped with reflux condenser and mechanical agitator, ammonium metavanadate (19.65g) is suspended in 218.54g50wt% two (2 hydroxy propanoic acid) two hydroxide two ammonium close in titanium (IV) solution and then add the preparation of 150mL deionized water.At room temperature under 700rpm, stir beige coloured suspension 10 minutes.Then slowly add the phosphoric acid of 105.06g85%, use the deionized water rinsing of about 50mL afterwards.Color becomes faint yellow immediately, then becomes green and in 20 minutes, becomes light green color again.Then suspension is added hot reflux one hour, do not observe the change of further color afterwards.Reactor is cooled in ice-water bath about 6 DEG C, adds the absolute ethyl alcohol of 700-800mL, cause mixture retrogradation.6 DEG C stir contents 20 minutes and while vacuumizing by solid collection on the frit of intermediate pore degree.Collect emerald green filtrate (405.28g) and carry out elementary analysis.
Allow the solid air drying of filtering to vacuumize on the frit to obtain shallow green powder simultaneously.First by within 16 hours, calcining this powder to obtain celadon solid in 300 DEG C of heating in atmosphere in Muffle furnace.Then this solid is divided by 8x14 mesh sieve.The granule of this 8x14 sieve mesh then in quartz tube furnace in 450 DEG C, the air of 60SCCM flows down calcining 6 hours to obtain the erose granule of light green color.
It is mainly unbodied that X-ray diffraction pattern (Fig. 9) shows catalyst.Surface property and total composition of the catalyst prepared in this embodiment gather in Table 1.Be lost in the vanadium in filtrate, titanium and phosphorus percentage to gather in table 2.Vapour phase condensation experiment is carried out according to embodiment 4.The performance of catalyst gathers in table 10.
This embodiment to prove that condensation by precipitating the V-Ti-P material that obtains catalysis formaldehyde and acetic acid effectively from ethanol is to form acrylic acid.Particularly, this catalyst maintained after 27 hours about 78% formaldehyde conversion and after same time about 80% selectivity of product.Filter the phosphorus component loss of vanadium component and the 15.5wt% only causing 7wt%.
embodiment 6
not using anti-solvent to prepare amorphous V-Ti-P catalyst by method J uses the reactor of liquid, aqueous charging to screen
The catalyst used in this embodiment first by the 1L tri-mouthfuls of tank reactors being equipped with reflux condenser and mechanical agitator, ammonium metavanadate (19.52g) is suspended in 218.34g50wt% two (2 hydroxy propanoic acid) two hydroxide two ammonium close in titanium (IV) solution and then add the preparation of 150mL deionized water.At room temperature under 700rpm, stir beige coloured suspension 10 minutes.Then slowly add the phosphoric acid of 105.32g85%, use the deionized water rinsing of about 50mL afterwards.Color is changing into faint yellow immediately, then becomes green and in 20 minutes, becomes light green color again.Then suspension is added hot reflux one hour, do not observe the change of further color afterwards.Reactor is cooled in ice-water bath about 6 DEG C, adds 800mL deionized water.6 DEG C stir contents 20 minutes and while vacuumizing by solid collection on the frit of intermediate pore degree.Collect navy blue filtrate (459.9g) and carry out elementary analysis.
Allow the solid air drying of filtering to vacuumize on the frit to obtain shallow green powder, this powder is first by being in air that in Muffle furnace 300 DEG C of heating calcining in 16 hours is to obtain celadon solid simultaneously.Then this solid is divided by 8x14 mesh sieve.The granule of this 8x14 sieve mesh then in quartz tube furnace in 450 DEG C, the air of 60SCCM flows down calcining 6 hours to obtain yellow erose granule.
It is mainly unbodied that X-ray diffraction pattern (Figure 10) shows catalyst.Surface property and total composition of the catalyst prepared in this embodiment gather in Table 1.Be lost in the vanadium in filtrate, titanium and phosphorus percentage to gather in table 2.Vapour phase condensation experiment is carried out according to embodiment 4.The performance of catalyst gathers in table 11.
This example demonstrates by not causing having the material of relative high titanium content containing isolated by filtration V-Ti-P catalyst under anti-solvent such as ethanol and losing vanadium and the phosphorus component of nearly 36wt%.In addition, it is effective not as the V-Ti-P material in embodiment 5 that the material obtained carries out condensation reaction.Such as, although the conversion ratio of formaldehyde starts height (>90%), to acrylic acid selective relatively low (after 27 hours about 59%).In addition, this reaction is at the low about 20wt% of 27 little productivity ratio embodiments 5 constantly.
Provide below being summarised in of the XRD measurement result of prepared catalyst.
the condensation reaction of embodiment 7-9
The catalyst used in these embodiments is that the 5.0g obtained by the catalyst batch of the present invention described in embodiment 3 feeds.Vapour phase condensation reaction carrying out like that as described in Example 3.In embodiment 7 and 8, change air speed, but the mol ratio of feed component keeps constant.Trioxane is counted three formaldehyde equivalents and inert material and count constituent of air outside nitrogen oxygen, the mol ratio of feed component acetic acid/formaldehyde/water/inert material/oxygen is 1.31/0.33/0.45/2.93/0.19.
At 16.02mL(17.3g) liquid charging after sample to minimize any impact that the catalysqt deactivation due to the induction of possible reactant causes.Then weigh and analyze sample.Last sample is got after liquid charging stops for one hour.Usually, under each set condition, get three samples, and result provides as the mean value of the result of the sample collected under every set condition.Result gathers in following table 12.After reaction under a given set condition completes, stand 10SCCM nitrogen at 405 DEG C by making it and add 20.8SCCM air after regenerating this catalyst yesterday.
embodiment 7
This embodiment illustrate preferable range compared with low-speed region in the invention carried out.Acetic acid/formaldehyde/water/inert material/the oxygen mixture of 1.31/0.33/0.45/2.93/0.19 mol ratio is delivered in reactor under these conditions under the air speed of all feed component/kg-hr of 60mol.Exothermic heat of reaction, and be 339.5 DEG C at this run duration catalyst bed temperature.Result gathers in following table 12.
embodiment 8
This embodiment is illustrated in the invention carried out in most preferred air speed region.Acetic acid/formaldehyde/water/inert material/the oxygen mixture of 1.31/0.33/0.45/2.93/0.19 mol ratio is delivered in reactor under these conditions under the air speed of all feed component/kg-hr of 138mol.Exothermic heat of reaction, and be 352.9 DEG C at this run duration catalyst bed temperature.Result gathers in following table 12.
embodiment 9
This embodiment is carried out under low-speed value outside the preferred scope of the present invention.Acetic acid/formaldehyde/water/inert material/the oxygen mixture of 1.31/0.33/0.45/2.93/0.19 mol ratio is delivered in reactor under these conditions under the air speed of all feed component/kg-hr of 26mol.Exothermic heat of reaction, and be 334.2 DEG C at this run duration catalyst bed temperature.Result gathers in following table 12.
Thus, high-speed condition of the present invention creates less acetic acid and destroys, higher space-time yield, higher acrylate productive rate by the formaldehyde equivalent of charging and Geng Gao by selective to acrylate of the formaldehyde reacted.The reduction that improvement in these performances is little on formaldehyde conversion, because the difference of formaldehyde conversion is mainly because the formaldehyde destroyed by reaction of the present invention is less.In addition, in business method, formaldehyde will be recycled.
embodiment 10
This embodiment illustrates preferred conditions permit high selectivity of the present invention and acidity keeps and do not need catalyst regeneration within the time period extended.The reactor setting of this embodiment and the similar of embodiment 7-9, except 2 differences.Employ a different stove, and the span reactor about 1.5 inches (3.8cm) of this stove.This setting result in than catalyst bed temperature lower in the previous embodiment.Stove is arranged on 320 DEG C, and during reaction catalyst bed temperature between about 327-332 DEG C.Second difference is that receiver remains on environment temperature instead of 0 DEG C.Acetic acid/formaldehyde/water/inert material/the oxygen mixture of 1.31/0.33/0.45/2.93/0.19 mol ratio is delivered in reactor under the air speed of all feed component/kg-hr of 138mol.Reaction runs continuously and does not interrupt or any catalyst regeneration.Two samples are collected at the first day of operation.Then a sample is collected every day.Following table 13 summarizes the performance in continued operation without any the 4th, 17 and 31 day the preferred method of the present invention of regeneration.
Following examples 11-25 illustrates the preparation of loaded catalyst of the present invention.Embodiment 26-37 demonstrates loaded catalyst of the present invention and is being prepared the effectiveness in acrylic acid by acetic acid and formaldehyde source.
embodiment 11
Solution is prepared by ammonium vanadate (0.97g, 8.29mmol), water (10mL) and oxalic acid (2.09g, 16.58mmol).Ammonium vanadate dissolves when not heating and releases gas to form blue solution.The solvable Ti source used in this embodiment be two (2 hydroxy propanoic acid) two hydroxide two ammonium close titanium (IV), 50wt%(TBALDH in water), identifiedly comprise 13.4wt%TiO 2.By 9.886g(0.0166molTi) TBALDH solution add in water-based V/ oxalic acid solution.This solution keep clarification blueness and without precipitation.Because discharge gas from solution, this solution will be used for flooding needs accurate weight.By weighing flask+agitator+solution deduct dry flask and the weight of agitator, the weight of solution is that 22.28g delivers in storage bottle by 22.42g().Every gram of this solution comprises the V(18.83mg of 0.3698mmol) and 0.7395mmolTi(35.42mg).The density of this solution is 1.15g/mL.
embodiment 12
Carry out a test how to show with the solution testing embodiment 11 when drying and dry material how with water-based H 3pO 4reaction.The solution of 1.560g embodiment 11 is placed in evaporating pan and heats in steam bath.This generates the glass (0.440g) of dark blue-green.With by the H of 0.401g85% being diluted with water to 1.3mL 3pO 4this glass of solution-treated prepared by (the amount 0.379g of calculating).Originally, the glass biodissolution of about 20% is to form clear green solutions, but then whole system becomes thick light green paste.
embodiment 13
Use a part of solution (4.08g) from embodiment 11 and TiO 21/16-inch extrudate (5.0g, AlfaAesar batch of #K21S005) prepares TiO 2the catalyst precarsor of load.These conditions are approximately just wet impregnation.After immersion, the TiO of white 2grizzle.By the TiO of dipping under stirring once in a while 2dry in steam bath.The dried material of steam bath is light gray.At 110 DEG C in Muffle furnace by this material dried overnight.After taking out from Muffle furnace, material is light gray-dark brown (lightgray-tan).Use phosphorus aqueous acid to add in catalyst precarsor by incipient wetness by phosphorus, the solution of preparation comprises enough phosphorus to obtain P/V mol ratio=5.5.The amount of the solution needed is calculated by the density measurement (1.15g/mL) of the solution of the embodiment 11 for the preparation of initial catalyst precarsor, makes the volume of phosphate aqueous solution identical with the solution of the embodiment 11 used at first.By the H of 0.996g85% being diluted with water to 3.5mL 3pO 4(the amount 0.992g of calculating) prepare solution and for dipping by Muffle furnace recycled materials.The impregnated material obtained is very light green.The sample of phosphate impregnation looks in incipient wetness shape and stirs until flow freely in its evaporating dish in steam bath with Teflon scraper.Color remains green, but when becoming more shallow tone after water evaporation.Sample is placed in Muffle furnace in its evaporating dish and be heated to 110 DEG C within 2 hours, be then heated to 450 DEG C 6 hours.The catalyst (5.912g) obtained is for yellow.
embodiment 14
Use a part from the solution (6.82g) of embodiment 11 and the SiO of 8 order Davison57 levels 2(5.0g, batch 557) prepares SiO 2the catalyst precarsor of load.These conditions are about just wet impregnation.The SiO of wet leaching 2for navy blue.Under stirring once in a while in steam bath this material dry.The dried material of steam bath is light blue.By this material dried overnight in Muffle furnace at 110 DEG C.After taking out from Muffle furnace, this material is navy blue.
Use phosphorus aqueous acid to add in catalyst precarsor by incipient wetness by phosphorus, the solution of preparation comprises enough phosphorus to obtain P/V mol ratio=5.5.The amount of the solution needed is calculated by the density measurement (1.15g/mL) of the solution of the embodiment 11 for the preparation of initial catalyst precarsor, makes the volume of phosphate aqueous solution identical with the solution of the embodiment 11 used at first.By the H of 1.654g85% being diluted with water to 5.9mL 3pO 4(the amount 1.658g of calculating) prepare solution and for dipping by Muffle furnace recycled materials.The impregnated material obtained is very dark green.
The sample of phosphate impregnation looks and is in just wet impregnation and stirs until flow freely in its evaporating dish in steam bath with Teflon scraper.Color remains green, but when becoming more shallow tone after water evaporation.Sample is placed in Muffle furnace in its evaporating dish and be heated to 110 DEG C 2 hours, be then heated to 450 DEG C 6 hours.The catalyst (6.572g) obtained is for having the green of orange areas and looking extraordinary image V/2Ti/5.5P oxide catalyst in bulk.
embodiment 15
Use a part of solution (7.24g) from embodiment 11 and high surface area alumina 1/8-inch extrudate (5.0g, AlfaAesar batch number A22M20, stock numbers 43832, bimodulus pore size distribution, the about 255m2/g of surface area) prepare the catalyst precarsor of alumina load.During preparation, add too much solution (9.094g), and a part (abandoning) removes to make the amount of solution to be left 7.24g with dropper.Under this amount of solution, catalyst is wet, but almost can't see solution on evaporating dish.When initial impregnation, catalyst precarsor is blue.It is dry in steam bath under stirring once in a while.The dried material of steam bath is light gray.By this material dried overnight in Muffle furnace at 110 DEG C.After taking out from Muffle furnace, this material is light gray-dark brown.
Use phosphorus aqueous acid to add in catalyst precarsor by incipient wetness by phosphorus, the solution of preparation comprises enough phosphorus to obtain P/V mol ratio=5.5.The amount of the solution needed is calculated by the density measurement (1.15g/mL) of the solution of the embodiment 11 for the preparation of initial catalyst precarsor, makes the volume of phosphate aqueous solution identical with the solution of the embodiment 11 used at first.By the H of 1.761g85% being diluted with water to 6.3mL 3pO 4(amount of calculation 1.760g) prepare solution and for dipping by Muffle furnace recycled materials.The impregnated material obtained is light green.
The sample of phosphate impregnation looks and is in just wet impregnation and stirs until flow freely in its evaporating dish in steam bath with Teflon scraper.Color remains green, but when becoming more shallow tone after water evaporation.Sample is placed in Muffle furnace in its evaporating dish and be heated to 110 DEG C 2 hours, be then heated to 450 DEG C 6 hours.The catalyst (6.802g) obtained is for light green and have some crackles in extrudate.
embodiment 16
The aqueous solution of following preparation V/Ti.Under stirring at room temperature ammonium vanadate (0.97g, 8.28mmol) and oxalic acid dehydrate (2.06g, 16.58mmol) are dissolved in water.The color of solution became red extremely brown extremely palm fibre/green (along with effusion bubble) to dirty-green to skipper from orange in one hour.After about other one hour of wait, can't see gas and overflow from blue solution.Based on the loss in weight of solution, the about gas of 240mg of having overflowed.Add TBALDH solution (9.89g, 16.6mmolTi) to produce dark blue solution (22.62g).Every gram of this solution comprises 0.3665mmolV (18.67mg) and 0.7339mmolTi (35.15mg).
The catalyst of zirconia load is prepared by this solution of a part (2.355g) and zirconia catalyst support (5.0=g, AlfaAesar batch of #B21T010) 1/8-inch extrudate.The moist catalysis of this amount close to just wet impregnation and in evaporating dish has nattier blue color.In steam bath, under agitation the material of dry dipping has the material of very light blueness with generation.This material is placed in Muffle furnace and at 110 DEG C dried overnight.Be light gray-dark brown by Muffle furnace recycled materials.
In theory, this catalyst comprises the V of 0.8631 equivalent, therefore for the second dipping needs 5.5 doubly to the phosphorus (4.747mmol) of this amount or 547.3mg 85% H 3pO 4.By the H of 85% of 547.3mg 3pO 4prepare solution and be diluted with water to volume=2.0mL.Be placed in clean evaporating dish by by Muffle furnace recycled materials sample and use H 3pO 4aqueous impregnation.For the condition of this dipping close to just wet impregnation (some liquid are also moistening evaporating dish).Under stirring with Teflon scraper, drying composite is until flow freely.The dried material of steam bath is light green and looks is uniform.It to be placed in Muffle furnace and at 110 DEG C dry 2 hours.
By Muffle furnace recycled materials be ash-dark brown.It to be stored in identical evaporating dish and in 450 DEG C of calcinings 6 hours in Muffle furnace.Be uniform yellow by Muffle furnace recycled materials (5.45g).
embodiment 17
The catalyst of this embodiment is designed to have approximately following ratio of adding material: V/Ti/P=1/2/5.5(ignores TiO 2carrier).Catalyst precarsor is at TiO 2the V of the 2.4wt% on extrudate, it is by moisture VCl 3with 1/16-inch TiO 2then extrudate preparation calcines 2 hours at 500 DEG C.This catalyst of 5.0g be placed in evaporating dish and close titanium (IV) (at water 50wt%(TBALDH) with 2.81g bis-(2 hydroxy propanoic acid) two hydroxide two ammonium, being accredited as the TiO comprising 13.4wt% 2) dipping, stir simultaneously.The TBALDH solution (about 2.3mL) of this amount is about just for just wet impregnation, and catalyst surface is wet, but does not have puddle in evaporating dish.V/TiO 2the initial charge packet of catalyst contains the V of about 2.356mmol, and this TBALDH solution comprises the about 4.71mmol of about 2 times of Ti(to this amount).The evaporating dish of V/TiO2 material comprising Ti dipping to be placed in Muffle furnace and 110 DEG C of heated overnight.The catalyst reclaimed by Muffle furnace has grey and initial V/TiO 2catalyst is Sandy.Be diluted to by water 2.3mL 85% H 3pO 4this material of impregnation mixture prepared by (1.49g, 12.96mmolP).This amount of solution is closely just wet impregnation also, although the end of evaporating dish is also wet.Evaporating dish is placed in steam bath and heats until extrudate presents drying under stirring once in a while.Evaporating dish is placed in Muffle furnace and at 110 DEG C dry 2 hours, then at 500 DEG C dry 6 hours.By Muffle furnace recycled materials (6.16g) compared with beginning V/TiO 2material (slightly aobvious ash-dark brown) dark brown darker.
embodiment 18
This embodiment illustrates the more concentrated V/Ti aqueous solution of use, and wherein ammonium vanadate and oxalic acid start and is not dissolved in (situation unlike embodiment 11) in water.This allow that first wet impregnation that these two kinds of metals are single is to provide about 2 times of useful loads on silica supports in such as embodiment 14.By ammonium vanadate (0.97g, 8.29mmol), two (2 hydroxy propanoic acid) two hydroxide two ammonium close titanium (IV) (in water 50wt% (TBALDH), the identified TiO containing 13.4wt% 2) (9.886gTBALDH solution, 16.6mmolTi) and oxalic acid dehydrate (2.09g, 16.58mmol) prepare solution.After one hour, obtain the dark blue solution of quality=12.89g.1 gram of this solution comprises the V(32.76g of 0.643mmol) and the Ti(61.69g of 1.288mmol).
By Davison8 order 57 grades of SiO 2(5.0g, batch 557) is loaded in evaporating dish.This SiO is loaded with the V/Ti aqueous solution (7.959g) 2to the point (the V useful load for about 5wt% needs 7.63g) of just wet impregnation.This material is stirred until dry and flow freely in steam bath.Then to be transferred in Muffle furnace and be heated to 110 DEG C 4 hours.By Muffle furnace recycled materials (8.454g) for light blue and dipping quite evenly (noticing that at the material of this stage embodiment 14 of method be navy blue).
Prepared solution by the phosphoric acid (3.245g, 28.147mmol) of 85% and be diluted with water to 5.9mL.The amount of this P is 5.5 molar excess in the amount of V on silica.The silica comprising V and Ti in evaporating dish is immersed in all phosphate aqueous solutions.The addition of 5.9mL is in excess in the amount (may exceed about 0.5mL) of just wet impregnation needs slightly.Catalyst becomes bottle green immediately and residual liquid part is green.By mixture in steam bath under agitation heating until material is free-pouring and when it is evaporated without any the sign precipitated in green liquid (showing the dissolubility to a certain degree of V in phosphate aqueous solution).The material of steam bath drying is light green and presents to flood quite uniformly.To be placed in Muffle furnace and at 110 DEG C heated overnight.The material (10.381g) obtained by 110 DEG C of Muffle furnaces is light green.By this material transfer of 10.326g in new evaporating dish, this material is placed in Muffle furnace and heats 6 hours at 450 DEG C.By reclaiming 8.194g green catalyst in Muffle furnace.
embodiment 19
Solution is prepared by ammonium vanadate (4.85g, 41.5mmol), oxalic acid (10.45g, 82.9mmol) and water (50mL).The initial mass of this solution is 64.91g, and the quality after gas effusion stops is 63.31g(loss 1.60g).The TBALDH aqueous solution (49.43g, 83.0mmolTi) is joined in this Ammonium Vanadate Solution.The quality obtaining solution is 112.76g.Every gram of this solution comprises the V(18.74mg of 0.368mmol as calculated) and the Ti(35.26mg of 0.736mmol).
Titanium dioxide silico briquette (50.02g, 8 orders, Davison57 level, batches 557) is placed in evaporating dish.By this solution of a part (76.43g) by the extremely just wet impregnation of the silica dipping in evaporating dish.In steam bath under stirring once in a while this mixture dry until to flow freely and light blue, then further in Muffle furnace in 110 DEG C of dried overnight.64.31g is reclaimed by Muffle furnace.This catalyst comprises the V of 28.13mmol.Every gram of V(22.28mg comprising 0.4374mmol).This catalyst is divided into the part of the 6g loaded for phosphorus, and therefore 6g charge packet is containing the V of 2.2244mmol.
A feature of the present invention is once V and Ti is on carrier, can prepare many different catalyst on a catalyst, as illustrated in embodiment 20-23 by using the phosphorus component of different amount to load.
embodiment 20
This embodiment illustrates the preparation of the oxide catalyst of V/2Ti/3.5P mol ratio.The catalyst of 6.0g embodiment 19 is placed in evaporating dish.Use by be diluted to 5.5mL 85% H 3pO 4this catalyst of solution impregnation prepared by (1.06g, 9.18mmolP) (dilution of 5.5mL provides the first wet impregnation of the catalyst precarsor to this amount).Steam bath is stirred this mixture until flow freely.Catalyst precarsor sample is placed in Muffle furnace and at 110 DEG C dry 1 hour.The catalyst of drying is transferred in clean evaporating dish, is back to Muffle furnace, then calcine 6 hours at 450 DEG C.Reclaim 5.789g.
embodiment 21
This embodiment illustrates the preparation of the oxide catalyst of V/2Ti/4.0P mol ratio.The catalyst of 6.0g embodiment 19 is placed in evaporating dish.Use by be diluted to 5.5mL 85% H 3pO 4this catalyst of solution impregnation prepared by (1.21g, 10.50mmolP).Steam bath is stirred this mixture until flow freely.Catalyst precarsor sample is placed in Muffle furnace and at 110 DEG C dry 1 hour.The catalyst of drying is transferred in clean evaporating dish, is back to Muffle furnace, then calcine 6 hours at 450 DEG C.Reclaim 5.855g.
embodiment 22
This embodiment illustrates the preparation of the oxide catalyst of V/2Ti/4.5P mol ratio.The catalyst of 6.0g embodiment 19 is placed in evaporating dish.Use by be diluted to 5.5mL 85% H 3pO 4this catalyst of solution impregnation prepared by (1.36g, 11.81mmolP).Steam bath is stirred this mixture until flow freely.Catalyst precarsor sample is placed in Muffle furnace and at 110 DEG C dry 1 hour.The catalyst of drying is transferred in clean evaporating dish, is back to Muffle furnace, then calcine 6 hours at 450 DEG C.Reclaim 5.999g.
embodiment 23
This embodiment illustrates the preparation of the oxide catalyst of V/2Ti/5.0P mol ratio.The catalyst of 6.0g embodiment 19 is placed in evaporating dish.Use by be diluted to 5.5mL 85% H 3pO 4this catalyst of solution impregnation prepared by (1.51g, 13.12mmolP).Steam bath is stirred this mixture until flow freely.Catalyst precarsor sample is placed in Muffle furnace and at 110 DEG C dry 1 hour.The catalyst of drying is transferred in clean evaporating dish, is back to Muffle furnace, then calcine 6 hours at 450 DEG C.Reclaim 6.085g.
embodiment 24
Preparation comprises the loaded catalyst of 5mol% vanadium and 10mol% phosphorus in the following manner: first basis is at I.C.Marcu etc., j. Mol. Catal., Vol.203, the step described in 241-250 page (2003) preparation has 100m 2white crystals Titanium pyrophosphate (the TiP of/g specific area 2o 7), then pulverize and divided by 8x14 mesh sieve.By ammonium vanadate (0.164g, 0.0014mol), 85%H 3pO 4(0.326g, 2.83mmol), water (10mL) and lactic acid (1.13g, 12.54mmol) prepare solution.Ammonium Vanadate Solution dissolves when not heating and forms green solution.Then this solution is joined the TiP of the 6.21g in 100ml single necked round bottom flask 2o 7in 8X14 mesh material (0.028mol).Then this flask be placed in the rotary evaporator with the water-bath being set as 65 DEG C and rotate 20 minutes in this bath under ambient pressure, within this time period, supernatant becomes blueness.Then under vacuo in 65 DEG C of dry flask contents and in atmosphere in 450 DEG C of calcinings 16 hours to obtain the erose particle of yellow green.
embodiment 25
Preparation comprises the loaded catalyst of 5mol% vanadium and 10mol% titanium and 10mol% phosphorus in the following manner: first basis is at I.C.Marcu etc., j. Mol. Catal., Vol.203, the step described in 241-250 page (2003) preparation has 100m 2white crystals Titanium pyrophosphate (the TiP of/g specific area 2o 7), then pulverize and divided by 8x14 mesh sieve.By ammonium vanadate (0.163g, 0.0014mol), TBALDH(1.67g, 2.84mmol), water (10mL) and lactic acid (1.13g, 12.54mmol) prepares solution.Ammonium Vanadate Solution dissolves when not heating and forms orange solution.Then this solution is joined the TiP of the 6.21g in 100ml single necked round bottom flask 2o 7in 8X14 mesh material (0.028mol).Then this flask be placed in the rotary evaporator with the water-bath being set as 65 DEG C and rotate 20 minutes in this bath under ambient pressure, within this time period, supernatant becomes green.Then at 65 DEG C, then vacuum drying flask contents adds 85%H 3pO 4the aqueous solution of (0.33g, 2.86mmol).The suspension obtained, then on the rotary evaporator in 65 DEG C of vacuum drying, then calcines 16 hours to obtain yellow erose particle in 450 DEG C in atmosphere.
embodiment 26-37
The loaded catalyst from embodiment 13-18 and 20-23 is used to carry out the acetic acid of embodiment 26-35 and the condensation reaction of trioxane (formaldehyde source) according to the step of comparative example 1 respectively.
The loaded catalyst from embodiment 24-25 is used to carry out the acetic acid of embodiment 36-37 and the condensation reaction of trioxane (formaldehyde source) according to the step of embodiment 1 respectively.
The vapour phase condensation experiment of embodiment 26-37 325 DEG C, the charging of 0.083mL liquid/minute and the N of 80SCCM 2under carry out three hours with the mol ratio charging (density 1.06g/mL) of 12 acetic acid/1 trioxanes.The performance of these catalyst is summarised in following table 14 and 15.The display of these embodiments can use the organic titanic compound of the redox active of water soluble to prepare load Qia V-Ti-P catalyst.Those skilled in the art will know that titanium chloride is unsuitable for flooding on solid carrier catalyst, the hydrochloric acid produced by titanium chloride hydrolysis is destructive for carrier material.
The present invention by being specifically described in detail with reference to its preferred embodiment, but being to be understood that and can carrying out within the spirit and scope of the present invention changing and revising.

Claims (17)

1. comprise a carbon monoxide-olefin polymeric for the amorphous mixed oxide of vanadium (V), titanium (Ti) and phosphorus (P), it has 30-60m 2the BET surface area of/g, wherein said titanium component derived from comprise two (2 hydroxy propanoic acid) two hydroxide two ammonium close the water soluble of titanium (IV), the organic titanic compound of redox-activity.
2. carbon monoxide-olefin polymeric according to claim 1, it has general formula VTi ap bo c, wherein a is the number of 0.3-6.0, and b is the number of 2.0-13.0; C is the atomicity needed for chemical valence meeting V, Ti and P.
3. carbon monoxide-olefin polymeric according to claim 2, wherein a is the number of 1.0-4.0, and b is the number of 4.0-10.0.
4. according to the carbon monoxide-olefin polymeric of any one of claim 1-3, wherein said carbon monoxide-olefin polymeric comprises preformed carrier further, wherein said preformed carrier comprises silica, aluminium oxide, titanium oxide, Titanium pyrophosphate, zirconia or zirconium pyrophosphate, and wherein said preformed carrier has the particle diameter of 0.1mm-20mm.
5. preparation comprises the method for the carbon monoxide-olefin polymeric of the amorphous mixed oxide of vanadium (V), titanium (Ti) and phosphorus (P), and described catalyst has 30-60m 2the BET surface area of/g, wherein said method comprises:
(a) providing package containing water soluble, the aqueous solution of the organic titanic compound of redox active, described organic titanic compound comprise two (2 hydroxy propanoic acid) two hydroxide two ammonium close titanium (IV);
B vfanadium compound and phosphorus compound join in the aqueous solution of this titanium to form the mixture of catalytic component by ();
C () heats this mixture;
D () removes water to obtain the solid residue comprising described catalytic component from heat-treated mixture; With
E () calcines this solid residue in the presence of air at elevated temperatures to obtain carbon monoxide-olefin polymeric.
6. method according to claim 5, wherein water remove step (d) comprise distillation or evaporation.
7. method according to claim 5, wherein water removes step (d) and comprises and anti-solvent to be joined to be settled out catalytic component and to isolate precipitation to obtain solid residue from liquid in described mixture,
Wherein by filtering precipitation and separation from liquid, wherein said anti-solvent is the polar compound being selected from alcohol, ketone, aldehyde, ether and ester.
8. method according to claim 7, wherein said anti-solvent is alcohol.
9., according to the method for any one of claim 5-8, wherein carbon monoxide-olefin polymeric has general formula VTi ap bo c, wherein a is the number of 0.3-6.0, and b is the number of 2.0-13.0; C is the atomicity needed for chemical valence meeting V, Ti and P.
10. method according to claim 9, wherein a is the number of 1.0-4.0, and b is the number of 4.0-10.0.
11. according to the method for any one of claim 5-8, and wherein said carbon monoxide-olefin polymeric comprises preformed carrier further and wherein joined in the mixture of catalytic component by described preformed carrier before heat treatment step (c).
12. according to the method for any one of claim 5-8, difunctional compound joins in the mixture of catalytic component before being included in heat treatment step (c) further by it, and wherein said difunctional compound comprises citric acid, lactic acid, glycolic, oxalic acid, ethylene glycol, butanediol, pentanediol or hexylene glycol.
13. methods according to claim 12, wherein said difunctional compound comprises lactic acid.
The method of 14. preparation 2,3-unsaturated carboxylic acids, comprising:
Under the existence of condensation catalyst, make formaldehyde contact with carboxylic acid to obtain 2,3-unsaturated carboxylic acid under vapour phase condensation condition, wherein vapour phase condensation condition comprises the combined feed air speed of 50-400mol charging/(kg catalyst hour);
Wherein said condensation catalyst comprises the amorphous mixed oxide of vanadium (V), titanium (Ti) and phosphorus (P), and has 30-60m 2the BET surface area of/g, and
Wherein said titanium component derived from two (2 hydroxy propanoic acid) two hydroxide two ammonium close the water soluble of titanium (IV), the organic titanic compound of redox-activity.
15. methods according to claim 14, wherein the source of formaldehyde comprises formaldehyde, 1,3,5-trioxane, dimethoxymethane or diethyl acyl-oxygen methane, and carboxylic acid comprises acetic acid or propionic acid.
16. according to the method for any one of claim 14-15, and wherein vapour phase condensation condition comprises the combined feed air speed of 100-300mol charging/(kg catalyst hour).
17. methods according to claim 16, wherein vapour phase condensation condition comprises the combined feed air speed of 125-200mol charging/(kg catalyst hour).
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